Alkylation



April 29, 1947.

ALKYLATION Filed Dec. 10, 1943 Recycle Acl'a' ISOBUTA/VE TOWER TIME TANK REA QTOR S 82 -3 DEPROMN/ZER lwparai'lblc Feed g/ILLER 4o WASH 26 nC4 In lbrfor 16 27 Amy/8% Inhibifor .20 25 Spenf Acid Fresh Ag [d I Affor-nqy Patented Apr. 29, 1947 Standard 1 y-ration ot lndiana Oil companmchicago, Ill., alcorpor j Bernard Shoemaker, Hammondp-i lnda and Bernard L.EveringnChicago lll -assignors to 1 ApplicationDece mber10, 1943,'SerialNo. 513,'l69

i l. scams. (or. 260 6834 The present invention "relates to a' process 511 reacting" olefins and olefin polymers with other hydrocarbons with-special reference to the progree V [byrnaint-aining within ductionifof saturated hydrocarbons; It pertains.

particularly toth'ealkylation of isoparafiins with an oleflnfisuchas ethylenefpropylene, butylenetv amy1ene,"for 'produ'cing' aviation gasoline and :3

niotor fuelsf'and the -alkylation of isoparaflinic'fl hydroc'arbonswiththepolymers of ethylene, propylene, butylene, etc., to produce high molecular weight saturated oils More particularly, the

controlled amount of anaromatic, suchtas henzene, as a cracking or .disproportionation inhibitor. sThe addition of a cyclic cracking inhibitor .lowers the rateof cracking and disproportion "tion, but does not adverselyefiect the rate of alkylationQtc a corresponding degreei The mechanism of: the reaction, however, is not clearlyunderstood and'we do not wish to be I boundzbyany theory of reaction. Nevertheless,

' it is a fact that the addition of controlled amounts presentfiinve tion s directed to a method fort; controlling the type ofprodutit by such a reaction.

is: known, that saturated hydrocarbons con- 1 taining tertiary'carbon atoms, hereinafter re-O ferrdftoas'fisoparaflins, will react with olefins and olefin polymers-"in the presence of various" by one orm re of H31, H01; BFz, SOe, H2O, etc. and'other catalysts of this'g'e'neraltype to produce! a widejrange of products.- 'The reactions involved are {e treniely coniplicated and I are little under-11 "Itis known that the nature of the reaction product will vary with the reaction conditions; witlfjthe type of mixture employed as startingJ materials, and with the particular catalystw selected. For a given feed and. for a given set.- of operating conditions-however, thenature of": the product produced; i.e., the-product distribu tion, bythe procedure heretofore followed is thee. yoiid'thcontrdl of the-operator. A broad objectof jourfinvention is to provide an improvement in: systehisbfflthis general type which offersimpor-S tant commercial advantages over any such 'proc-d.

Stood."

ess heretofore known'to theart". I i a *Iso'paraflins and menus undergo reactions in the. presence'iaf the alkylation catalysts to produce a variety" of product's' chiefly: parafiinic hydrocar boris "of branched chain'structure; Prior toiour. invention however, such conversions t. have. re;-.-v

sulted incons'idera1ble amounts oft cracking, disproportionation, or other side reactions, so that the conversion of a narrow boiling. ran echarging stock has'resulted in a relatively wide boiling range p'roduct; :This'istparticularly undesirable inthe production of aviation fuel components since the products of cracking: and 'dispropor-y tionation are of' lower octane number than {the alkylate, particularly those boiling above the--de-,-

sir'ed-alkylate- In addition, the side reactions apparently decrease the -life of the alkylation catalyst! r I According to thepresent invention, the product distribution is controlled to a very. desirable deacid 'alkylation catalysts; such as sulfuric I acid, h'y' v ozenfluoride-- and mineral 'acids activated ofzthesematerials reS ltSir mp e yields o the desired allitylate.-v It' is, therefore an bie like. A further object of our invention isto direct the hydrocarbon conversions primarily toward,

alkylationand to avoid such side reactions as the cracking; of charging stock and products to low molcculariweight hydrocarbons or the conversion otchargingstock into higherimolecular weight.

hydrocarbons than desired or to produce Products of unsatisfactory octane number. Another object issto'gprolong catalyst activity and catalyst life,

or,; inother;words,,toproduce a larger yield of desirable alkylation products per pound of cataa- Q lyst material than has heretofore been possible.

We. attainthese and other objects, which will be apparentas the detailed description of the inven- 3 tion proceeds, by efiectinga alkylation of hydrocarbons in the. presence of va .disproportionation or cracking; inhibitor 1 comprising, an aromatic.

Weycontemplate using aromaticssuch as benzene to control the side reactions occurring simultaneously with alkylation when using acid type' catalysts such as sulfuric acid, activated sulfuric acid; hydrogen fluoride, and acids activated with H51, H61, on s a. 10, et

.4 al 1 aromatics. are equally desirable as inhibitors, their effectiveness apparently depending on the availability. of the carbon atoms in the ring structure to which an alkyl may attach;

Thus--ghexaalkyl benzenes are "ineffective. Their. effectivenessincreases as the n'umber of alkyl groups attached-to the ring] is decreased with benzene being the most-desirable. ,vwhen o r i h ito that more drastic reaction conditions. can be employed. thereby obtaining a'process which is rnpreeiiidnt and less, sensitive to operating conditions. Our mventio'n'makee it possible to use srnaller reactors, higher concentrations of catalystvhigher temperatures, catalysts of wider the reaction zone a are used, we contemplate ranges of activity, etc. Thus our process has the advantage of being less sensitive to the operating conditions and the need of special control equipment is minimized.

In practicing our invention we efiect the alkylation of isop'araflins and olefins in the presence of the selected catalyst while maintaining in the alkylation zone a small critical amount 01 an inhibitor. A preferred example of such inhibitor is an aromatic hydrocarbon such as benzene. Thus benzene may be added in small critical amounts with the alkylation charge or separately and by using such inhibitors we may employ even more severe reaction conditions and catalyst of a wider range of activity without causing an undue amount of cracking.

The invention will be more clearly understood from the following example, and the detailed description read in conjunction with the accompanying drawing which forms a part of this specification and which is a schematic flow diagram of an embodiment of an alkylation system employing the cracking or disproportionation.

inhibitor.

As isoparaffinic hydrocarbons suitable for our process we can employ low boiling isoparafiins such as isobutane, isopentane, isohexane, or mixtures of any two or more of these hydrocarbons either with or without the correspondingnormal paratffins. The olefins can comprise such olefins as ethylene, propylene, the butylenes and amylenes or may include higher boiling olefins or polymers. The term butylenes as employed in the description of our process is intended to include either the normal butenes or isobutylene or mixtures thereof. a

A substantial molar excess of isoparaflins to olefins should be maintained within the reaction zone. The eiiluentproduct stream leaving the alkylation step is substantially free from olefins and the alkylate is separated from the lower.

boiling parafiins. The paraffins are fractionated to give an isoparaffin recycle stream for the alkylation step. Any normal parafiin can be recycled to an isomerization step which may supply the isoparaffin for the alkylation. The inhibitors can optionally be cycled with the normal parafiins to the isomerization step where they are likewise advantageous. It is also contemplated that the inhibitor and/or its reaction products can be included beneficially in the alkylate fraction.

The drawing illustrates one modification of our invention wherein isooctane is produced by the alkylation 'of isobutane with butylenes in the presence of strong sulfuric acid as the catalyst. Similar apparatus may be used in the alkylation of isobutane or other low boiling isoparafiin with propylene or amylenes. Likewise other catalysts can be used. Isoparaifinic feed may be introduced by line I0 into the system. If desired, the feed may have been prepared by passing through a feed preparation tower to remove any pentanes, etc., followed by caustic wash of the feed before being introduced into the isobutane line H. Alternatively the fresh feed can be introduced into the product wash and isobutane systems. Isobutane, feed and recycle, are passed by line H into chiller l2. Olefin feed is introduced by line l3, passed through chiller l4, line 40,

and mixed with the isobutane from 39. The

mixture of isobutane and olefin is then introduced'by line 11 into the emulsion recycle line 18. If desired olefins can be introduced between stages by line 38. The external or feed ratio of isoparaifin to olefin is maintained at about 4:1.

tank l6. In the operation of the unit for alkylating olefinic hydrocarbons and isobutane, low temperatures such as 35 and 50 F. are desirable to obtain good yield and product quality. The reaction temperature ordinarily will be at about 40 F. with a maximum of about 50 F. for butylene alkylation and about 60 F. for amylenes when acid concentrations are between about and These temperatures may be increased considerably when the oyclic hydrocarbon inhibitors are added in accordance with our invention. Likewise acids of lower strength can be used. Ordinarily, however, the second reactor will be at a higher temperature than the first and we contemplate introducing a cyclic cracking or disproportionationinhibitor by line 24. The inhibitor also may be introduced by line 25 along with the fresh feed to the alkylation. We contemplate using between about 0.05 and 2.5% preferably about 0.1 to 1.5% by volume of arcmatic, such as benzene, based on reactor hydrocarbon charge.

The efiluent from reactor I6 is split with a portion of the hydrocarbon-acid emulsionbeing passed by line 26 into settler 21. The balance of the emulsion is recycled by line l8 and line 22 to time tank IS. The acid emulsion is maintained at about 40 to 50% acid. Within settler 21 the recycle acid is separated, withdrawn by line 28 and returned to the reactor system by line 18. The acid strength is maintained above about 85%, spent acid being periodically or continuously withdrawn by valved line 31. The hydrocarbon fraction is withdrawn from settler 21 by line 29 and subjected to a caustic wash diagrammatically illustrated at 30. The concentration of isobutanein the reactor eiiiuent is maintained at about 30 to 40%. The alkylate and unreacted hydrocarbons are introduced by line 3| into isobutane tower 32. Normal butane and alkylate are withdrawn by bottom drawofi' line 33, the unreacted hydrocarbons being withdrawn overhead by line 34 and introduced into depropanizer 35. Propane is withdrawn over-,

tion of white oils by alkylating olefin polymers with an isoparafiin such as isobutane or isopentane, is the tendency for the polyolefin to be depolymerized. We contemplate the inclusion of benzene as cracking, disproportionation and depolymerization inhibitors in the alkylation of olefin polymers to make white oils. Thus a plant butane stream which ordinarily comprises a mixture of isobutylene, n-butylene, n-butane and isobutane is contacted with a polymerization cata-' lyst and the unsaturated hydrocarbons in the C4 stream are rapidly polymerized. The average molecular weight or the polymermay vary from about sec to 1000 depending upon the temperature of polymerization. These polymers on contact with an isoparafiin in the presence of an acid alkylation catalyst can be converted to saturated hydrocarbons. If desired, the polymerization and alkylation' may be carried out in series in separate towers with extraneous isobutane or isopentane introduced only into the second reaction zone. In another modification the total reaction is conducted within a single elongated zone with additional isoparaffin being introduced at vertically spaced points. It is also contemplated that only a fraction of the total polymer may be slowly added to a well agitated mixture of isoparafiin, catalyst and inhibitor such as benzene. In any case a renewed quantity of the aromatic hydrocarbon inhibitor is maintained within the zone wherein the alkylation occurs and thereby inhibits depolymerization of the relatively high molecular weight olefinic polymer. When the olymer is produced in a separate zone and only a fraction is used in the alkylation, the off-gases from the polymerization are a suitable source of isoparaffins for the alkylation step.

It is contemplated that modifications in the apparatus and process other than those described above and illustrated in the drawing can be made so as to obtain the optimum results with the selected type of alkylation catalyst. In each case, however, means should be provided for maintaining the inhibitor within the alkylation zone, the inhibitor being introduced at one or more points in the system, either independently or blended with one of the other fluids introduced into, with= drawn from, or circulated in, the. system. Various means for obtaining the desired temperature control, degree and time of contact with the catalyst, high isoparamn to olefin ratio, etc., can be used without departing from our invention. Hence, the chilling can be supplied by indirect refrigeration with propane or ammonia or by direct auto-refrigeration or indirect chilling with butanes as the refrigerant. Additional pressuring and/or cooling means can be provided to maintain the selected alkylation catalyst in the liquid phase during the contacting. Likewise a plurality of parallel time tanks may be used in series on the isoparafiln and in parallel on olefins. The acid cycle may be in series on fresh acid and parallel on recycle acid. The reactor itself may be of various types and it should be understood that we contemplate the use of various continuous reactors either of the agitator, the ciroulator-mlxer, the tower, or the jet and time tank types. For example, it may be a contactor of the type described in U. S. Patent 2,238,802. In any of the systems the contactors may be provided with means for bottom withdrawal of the catalyst.

Therefore, although we have described in more or less detail preferred embodiments of our invention, it should be understood that the in vention is not limited to any of the details hereinabove set forth and that we contemplate modifications of the invention which will be apparent from the above description to those smiled in the art. 1

We claim:

1. .Ifhe method or synthesizing hydrocarbons boiling within a narrow range which method comprises contacting isoparamnic and olefinic hydrocarbons with a mineral acid alkylation catalyst at a temperature of between about 40 and 60 F. a first contacting zone, withdrawing the reaction mixture from said first contacting step, supplying the withdrawn reaction mixture to a second contacting zone, commingling between about 0.1 and about 1.5 per cent of benzene, based upon the volume of total hydrocarbons supplied to the second contacting zone, with the reaction mixture and contacting the reaction mixture and added benzene in the second contacting zone at a temperature substantially above that employed in the first contacting step, the added benzene inhibiting the normal tendency for the alkylation catalyst to disproportionate the alkylation product at the higher alkylation temperature.

2. The method of synthesizing hydrocarbons which comprises maintaining a first pool of a mineral acid alkylation catalyst within a first contacting zone at a temperature of between about 40 and 60 F., maintaining a. second pool 'of a mineral acid alkylation catalyst of lower alkylating activity within a second contacting zone at a temperature appreciably above that in the first contacting zone, introducing isoparafiinic and olefinic hydrocarbons into said first contacting zone, transferring reaction mixture from said first contacting zone to said second contacting zone, introducing olefinic hydrocarbons into said second contacting zone, introducing into said reaction mixture between about 0.1 and about 1.5 per cent by volume of an alkylatable aromatic based upon the volume of total hydrocarbons supplied to the second alkylation step whereby side reactions resulting from cracking and disproportionation of the alkylate at the higher temperature are minimized, efiecting alkylation of at least a portion of said aromatic with a portion of the added olefinic hydrocarbons and recovering from the reaction products a liquid fraction including isoparaflinic and aromatic alkylate.

3. The method of synthesizing hydrocarbons boiling within a narrow range which comprises the steps of contacting a molal excess of isoparamns with olefins in the presence of sulfuric acid alkylation catalyst at a temperature of between about 40 and about 60 F. whereby substantially all of the olefinic hydrocarbons are consumed and the activity or the alkylation catalyst is diminished, withdrawing the total reaction mixture from the contacting step, adding olefinic hydrocarbons to the reaction mixture and introducing the reaction mixture and olefins into a sec ond contacting step, maintaining within said second step between about 0.1 and 1.5 per cent by volume of benzene based upon the volume of total hydrocarbons introduced into said second step, efiecting alkylation of isoparamnsand aromatics with olefins in said second step at a temperature substantially above that employed in the first stage whereby the normal tendency for the alkylation catalyst to disproportionate the alkylation product is inhibited, and recovering from the reaction products a liquid fraction including isoparaifinic and aromatic alkylate boiling within a narrow range.

BERNARD H. SHOEMAKER. WARD L. nvnnmo.

nnrnnnncns crrnn The following references are of record in the file of this patent: 

